CA1099100A - Heat-sensitive recording composition with mixed color precursors - Google Patents
Heat-sensitive recording composition with mixed color precursorsInfo
- Publication number
- CA1099100A CA1099100A CA298,181A CA298181A CA1099100A CA 1099100 A CA1099100 A CA 1099100A CA 298181 A CA298181 A CA 298181A CA 1099100 A CA1099100 A CA 1099100A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
HEAT-SENSITIVE RECORDING COMPOSITION
WITH MIXED COLOR PRECURSORS
ABSTRACT OF THE DISCLOSURE
A heat sensitive recording member capable of acquiring a stable color in selected regions contrasting with the background color of the coated substrate upon exposing these regions to an elevated temperature and comprising a paper or polymeric film substrate and a heat sensitive coating comprising (1) an adduct or mixture of color-forming lactones or spiropyrans with a cyclic polyketo color precursor, (2) a polymeric binder which bonds the reactants to the substrate and optionally (3) a molecular complex between a phenolic compound and an amine and/or an activator to lower the temperature of color formation.
WITH MIXED COLOR PRECURSORS
ABSTRACT OF THE DISCLOSURE
A heat sensitive recording member capable of acquiring a stable color in selected regions contrasting with the background color of the coated substrate upon exposing these regions to an elevated temperature and comprising a paper or polymeric film substrate and a heat sensitive coating comprising (1) an adduct or mixture of color-forming lactones or spiropyrans with a cyclic polyketo color precursor, (2) a polymeric binder which bonds the reactants to the substrate and optionally (3) a molecular complex between a phenolic compound and an amine and/or an activator to lower the temperature of color formation.
Description
BACKGROUND OF THE INVEN~ION
This invention relates to recording members containing heat-reactive components and, more particularly, to recording members capable of being used in thermographic copying, thermal printing, event recordin~, and as trans-parencies for overhead pro~ection.
Heat sensitive sheets containing the cyclic polyketo compounds of this invention, useful ~or copying and recording and characterized by an ability to form a mark of contrasting color when heated to an activation temperature of 50C, are known in the art. They are used in thermographic processes wherein a recording member is positioned on a graphic original and exposed to infrared radiation to cause a selective heating of the dark areas of the original sufficient to form a copy thereof on the heat sensitive member. The thermally responsive members have also been used to record the heated portions of a thermal print-head and to record a colored trace when contacted by the hot stylus of a thermal recorder.
The ninhydrinamine reaction wherein ninhydrin reacts with amino acids, primary amines, and certain derivatives of mor-pholine, piperidine, and pyrrolidine to give the dye commonly referred to as Ruhrman's purple is well known. Isatin reacts with these same amines to give isatin blue. Alloxan reacts with the amines to give a red dye. These rea~tions have been used in numerous inventions for thermally responsive copy and recording papers and films. Lawton, U. S. Patent No.3,736,166 used ninhydrin with various morpholine and piperidine derivatives to prepare transparencie~ for overhead projection. Lawton, U.S. Patent No~3,293,061 combined ninhydrin or hydrindantin with isatin-amine condensates to provide thermographic copy sheets~ ~auman and Lawton reacted ninhydrin or hydrindantin with complexes of amines and flavans or phenolic compounds to make thermographic copy sheet~, see u. S. Patent No.3,149,9gl and U. S. Patent No.3,149,992.
Huffman, U.S. Patent No.3,664,a5~ combined ninhydrin with the adducts of morpholine or piperidine and organic acids in thermal recording members. Sus, U.S. Patent No.3,024,362 combined hydrindantin with amino acids or salts of primary ~nines with organic carboxylic and sulfonic acids to make a thermocopy paper. Allen, U.S. Patent No.2,967,785 used the adducts of morpholine or piperidine with isatin or ninhydrin as the color forming material in thermocopy papers. Small, U.S. Patent No.3,573,958 combined an amine with a halide or organometallic halide of germanium, silicone, lead, and tin with hydrindantin to provide a heat sensi~ive recording sheet. In each case the normal dye formations of Ruhrman's purple with ninhydrin, red dye with alloxan, and isatin blue were obtained.
It is often desirabl~ and an objective of this invention to obtain colored records which have colors differing from those normally obtained with the above cyclic polyketo compounds.
Undesirable odors and fumes are obtained by the heat dissociation or decomposition of the complexes, salts, or adducts during the imaging process. There is a problem of image bleaching during excessive heating, on aging, or prolonged exposure to ultxaviolet containing light.
Other types of heat sensitive recording sheets are also well known in the art. This invention is related to the use of a leuco or colorless fo~n of a dye material and a phenolic material which reacts with the leuco material to form a colored dye. There are many systems of this type represented in the ~atent literature.
References ~or these systel~s include:
(1) ~hthalides, naphthalides, fluorans Typical of these are Crystal Violet Lactone or 3,3-bis-(p-dimethylaminophenyl)-6-dimethylamino phthalide and malachite green lactone or 3,3-bis(p-dimethylaminophenyl-phthalide). The reactions of these and many related phthalides with phenolics are d~escribed in Adachi, U.S.
Patent No.3,895,173; Schwab, U.S. Patent No.3,322,557;
Kohmura et al., U. S. Patent No.3,859,112; Hayashi et al., U.S. Patent No.3,773,542; Futaki et al., U.S. Patent No.
3,846,153; Baum, U.SO Patent No.3,539,375; Shimazu, U.S.
Patent No.3,864,684; Adachi et al., U~ S. Patent No.3,843,384;
Futaki et al., U.S. Patent No.3,829,401; Futaki et al., U.S. Patent No.3,825,432; Higachi et al, U.S. Patent No.3,816,838; Nagashima et al., U-.-S. Patent No.3,792,481;
Blose et al., U.S. Patent No.3,746,675.
Typical examples of the lactones which are listed in the patents as reacting with phenolic materials to produce a color include the following:
TABLE
3,3-bis~p-dimethylamillophen~ 6-dimethylaminophthalide 3,3-bis(p-dimethylamillophenylphthalide) 3,3-bis[p-di(n-butylaminopheny~)phthalide~
Rhodamin~. lact~ne 3-[2-methyl 4-~diethylamino)phenyl] 3-(1,2-dimethyl--3-indolyl)phthalide 3-(p-dimethylaminophenyl)-3~ ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide 3,3-bis(l~ethyl-2-methylindol-3-yl)phthalide 3-(4-morpholinophenyl)-3-~1,2-dimethylindol-3-yl)-4,5,6,7-tetrachlorophthalide 3~ benzyl-2-methylindol-3-yl)-8-(methyl-2-methylindol-3-yl~phthalide 5-nitro-3,3-bis~4-dimethylaminophenyl)phthalide 5-amino-3,3-bis(4-dimethylaminophenyl)phthalide 5-benzoylamino-3,3-bis-(4-dimethylaminophenyl)phthalide 3,3-bis(p-dimethylaminophenyl)-4,5,6~7-tetrachloro-phthalide 3,3-bis(p-diethylaminophenyl)-6-dimethylaminophthalide 3,3-bis(p~dimethylaminophenyl)-6-aminophthalide 3,3-bislp-dimethylaminophenyl)-6-(p-toluenesulfonamide) phthalide 3,3-bis~p-dimethylaminophenyl)-6-nitrophthalide 3,3-bis(p-dimethylaminophenyl)-6-monethylaminophthalide 3,3-bis~p-dimethylaminophenyl)-S-chlorophthalide 3,3-bis(p-dimethylaminophenyl)-6-ethoxyphthalide 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide 3-(4-diethylaminophenyl)-3-(1,2-dimethylindol-3-yl) naphthalide 3-(4-diethylaminophenyl)-3~ phenylpyrrol-3-yl) naphthalide 3-diethylamino-7-dibenzyl~minofluo~an 3-diethylamino-7-(N-methylanilino)fluoxan 3-dimethylamino-6~methoxyfluoran 3-diethylamino-6-methyl-7-ehlorofluoran 3-morpholino-5,6~ben~ofluoran 7-acetamino~3 dimethylaminofluoxan 3-dimethylamino 5,7 dimethy~fluoran 3,6-bis~ ~-methoxyethoxyfluoran 3,6-bis-~ -cyanoethoxyfluoran l-amino~3,6,7-trimethylfluoran 3-dibutylamino-6 methyl~7 chloro1uoran 3-diethylaminoo7-dihenzylaminofluoran 3-diethylamino /-(N-methyl-p-toluidino)fllloran 3-dimethylamino-7-chlorofluoran 3-(diethylamino)-6-methyl-7-anilinofluoran 3,7-bis~diethylamino)fluoran 3,6-dimethoxyfluoran 3-diamylamino-6-chlorofluoran
This invention relates to recording members containing heat-reactive components and, more particularly, to recording members capable of being used in thermographic copying, thermal printing, event recordin~, and as trans-parencies for overhead pro~ection.
Heat sensitive sheets containing the cyclic polyketo compounds of this invention, useful ~or copying and recording and characterized by an ability to form a mark of contrasting color when heated to an activation temperature of 50C, are known in the art. They are used in thermographic processes wherein a recording member is positioned on a graphic original and exposed to infrared radiation to cause a selective heating of the dark areas of the original sufficient to form a copy thereof on the heat sensitive member. The thermally responsive members have also been used to record the heated portions of a thermal print-head and to record a colored trace when contacted by the hot stylus of a thermal recorder.
The ninhydrinamine reaction wherein ninhydrin reacts with amino acids, primary amines, and certain derivatives of mor-pholine, piperidine, and pyrrolidine to give the dye commonly referred to as Ruhrman's purple is well known. Isatin reacts with these same amines to give isatin blue. Alloxan reacts with the amines to give a red dye. These rea~tions have been used in numerous inventions for thermally responsive copy and recording papers and films. Lawton, U. S. Patent No.3,736,166 used ninhydrin with various morpholine and piperidine derivatives to prepare transparencie~ for overhead projection. Lawton, U.S. Patent No~3,293,061 combined ninhydrin or hydrindantin with isatin-amine condensates to provide thermographic copy sheets~ ~auman and Lawton reacted ninhydrin or hydrindantin with complexes of amines and flavans or phenolic compounds to make thermographic copy sheet~, see u. S. Patent No.3,149,9gl and U. S. Patent No.3,149,992.
Huffman, U.S. Patent No.3,664,a5~ combined ninhydrin with the adducts of morpholine or piperidine and organic acids in thermal recording members. Sus, U.S. Patent No.3,024,362 combined hydrindantin with amino acids or salts of primary ~nines with organic carboxylic and sulfonic acids to make a thermocopy paper. Allen, U.S. Patent No.2,967,785 used the adducts of morpholine or piperidine with isatin or ninhydrin as the color forming material in thermocopy papers. Small, U.S. Patent No.3,573,958 combined an amine with a halide or organometallic halide of germanium, silicone, lead, and tin with hydrindantin to provide a heat sensi~ive recording sheet. In each case the normal dye formations of Ruhrman's purple with ninhydrin, red dye with alloxan, and isatin blue were obtained.
It is often desirabl~ and an objective of this invention to obtain colored records which have colors differing from those normally obtained with the above cyclic polyketo compounds.
Undesirable odors and fumes are obtained by the heat dissociation or decomposition of the complexes, salts, or adducts during the imaging process. There is a problem of image bleaching during excessive heating, on aging, or prolonged exposure to ultxaviolet containing light.
Other types of heat sensitive recording sheets are also well known in the art. This invention is related to the use of a leuco or colorless fo~n of a dye material and a phenolic material which reacts with the leuco material to form a colored dye. There are many systems of this type represented in the ~atent literature.
References ~or these systel~s include:
(1) ~hthalides, naphthalides, fluorans Typical of these are Crystal Violet Lactone or 3,3-bis-(p-dimethylaminophenyl)-6-dimethylamino phthalide and malachite green lactone or 3,3-bis(p-dimethylaminophenyl-phthalide). The reactions of these and many related phthalides with phenolics are d~escribed in Adachi, U.S.
Patent No.3,895,173; Schwab, U.S. Patent No.3,322,557;
Kohmura et al., U. S. Patent No.3,859,112; Hayashi et al., U.S. Patent No.3,773,542; Futaki et al., U.S. Patent No.
3,846,153; Baum, U.SO Patent No.3,539,375; Shimazu, U.S.
Patent No.3,864,684; Adachi et al., U~ S. Patent No.3,843,384;
Futaki et al., U.S. Patent No.3,829,401; Futaki et al., U.S. Patent No.3,825,432; Higachi et al, U.S. Patent No.3,816,838; Nagashima et al., U-.-S. Patent No.3,792,481;
Blose et al., U.S. Patent No.3,746,675.
Typical examples of the lactones which are listed in the patents as reacting with phenolic materials to produce a color include the following:
TABLE
3,3-bis~p-dimethylamillophen~ 6-dimethylaminophthalide 3,3-bis(p-dimethylamillophenylphthalide) 3,3-bis[p-di(n-butylaminopheny~)phthalide~
Rhodamin~. lact~ne 3-[2-methyl 4-~diethylamino)phenyl] 3-(1,2-dimethyl--3-indolyl)phthalide 3-(p-dimethylaminophenyl)-3~ ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide 3,3-bis(l~ethyl-2-methylindol-3-yl)phthalide 3-(4-morpholinophenyl)-3-~1,2-dimethylindol-3-yl)-4,5,6,7-tetrachlorophthalide 3~ benzyl-2-methylindol-3-yl)-8-(methyl-2-methylindol-3-yl~phthalide 5-nitro-3,3-bis~4-dimethylaminophenyl)phthalide 5-amino-3,3-bis(4-dimethylaminophenyl)phthalide 5-benzoylamino-3,3-bis-(4-dimethylaminophenyl)phthalide 3,3-bis(p-dimethylaminophenyl)-4,5,6~7-tetrachloro-phthalide 3,3-bis(p-diethylaminophenyl)-6-dimethylaminophthalide 3,3-bis(p~dimethylaminophenyl)-6-aminophthalide 3,3-bislp-dimethylaminophenyl)-6-(p-toluenesulfonamide) phthalide 3,3-bis~p-dimethylaminophenyl)-6-nitrophthalide 3,3-bis(p-dimethylaminophenyl)-6-monethylaminophthalide 3,3-bis~p-dimethylaminophenyl)-S-chlorophthalide 3,3-bis(p-dimethylaminophenyl)-6-ethoxyphthalide 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide 3-(4-diethylaminophenyl)-3-(1,2-dimethylindol-3-yl) naphthalide 3-(4-diethylaminophenyl)-3~ phenylpyrrol-3-yl) naphthalide 3-diethylamino-7-dibenzyl~minofluo~an 3-diethylamino-7-(N-methylanilino)fluoxan 3-dimethylamino-6~methoxyfluoran 3-diethylamino-6-methyl-7-ehlorofluoran 3-morpholino-5,6~ben~ofluoran 7-acetamino~3 dimethylaminofluoxan 3-dimethylamino 5,7 dimethy~fluoran 3,6-bis~ ~-methoxyethoxyfluoran 3,6-bis-~ -cyanoethoxyfluoran l-amino~3,6,7-trimethylfluoran 3-dibutylamino-6 methyl~7 chloro1uoran 3-diethylaminoo7-dihenzylaminofluoran 3-diethylamino /-(N-methyl-p-toluidino)fllloran 3-dimethylamino-7-chlorofluoran 3-(diethylamino)-6-methyl-7-anilinofluoran 3,7-bis~diethylamino)fluoran 3,6-dimethoxyfluoran 3-diamylamino-6-chlorofluoran
2',6'-bistdiethylamino1flu~ran 2'-~benzylamino)-6'-~di~thylamino)-3',4"-henzofluoran
3-(ethyl-p-tolylamino)-7-(methylphenylamino~fluoran 3-cyclohexylamino-6-chloro~luoran 3-diethylamino-5-methyl-7-bis(4-methyl~enzyl)aminofluoran 3-diethylamino 6-methyl-7-(p-butylanilino~fluoran 2'-anilino-6'-die~'nylamino-3'-methylfluoran 3-(diethylamino)-7-(N-methylanilino~fluoran 2'-phenylamino-3' methyl-6'-~N-ethyl-N-p-tolylamino) fluoran 3-diethylamino-7-piperidinofluoran 3-diethylamino 7-phen~lfluoran 3-diethylamino-5-chloro-7-piperidinofluoran 3 dimethylamino-5-methyl-7~piperidino,fluoran 3-diethylamino-5-methyl 7-piperidino~luoxan 2-(2',4'6'-trimethylphenylamino)-8-diethylamino-3,
4-benzofluoran 2,8-bis(N-ethyl-N-p-tolylamino)fluoran 3~diethylamino-6-methyl--7-o-anisidinofluoran 3-~diethylamino)-6,7~dimethylfluoran 3 dimethylamino~5-methy:L-7-Cbis-t4-methylbenzyl)aminol fluoran 4-amino~8 ~bis- B-ethoxyethyl)amino]benzo~luoran N,N'-bis (3'-diethyl~minofluoran~7'yl)piperazi.ne 2-phenylarnino-6-diethylamino1uoran 2-phenylamino-6-dimethylaminofluoran 3'-diethylamino-7'-methylthiofluoran 3,7-bis (diethylamino)-5,6-benzofluoran 3-dimethylamino-7-benzylamino~5,6 ben~ofluoran 3-diethylamino-7-(N-benzyl-N-phenyl)aminofluoran 3-benzylamino 7-diethylaminofluoran 2'-~p-chloroanilino)-6'-diethylaminofluoran 2'-tm-chloroanilino)-3-methyl-6l-diethylaminofluoran 2'-(p-chloro-N methylanilino)-6'-diethylaminofluoran 3 (diethylamino)-5-methyl-7-t~ -phen~lhydrazino~fluoran 3-(diethylamino~-7-bis(l-naphthylmethyl)aminoflUoran 3-tdiethylamino)-7-(2-ph~halimidino)1uoran 3-~diethylamino)-6-methyl-3'-azafluoran 3-diethylamino-5-methyl-7-(diphenylamino~fluoran 3-~dim~thylamino3-7-tdiphenylmethylamino)fluoran 3-(diethylamino~-6-methyl 7-(p,p'-dimethyldiphenyl-methyl)amino fluoran 3-tdibutylamino)-7-(diphenylmethylamino)fluoran 3-(diethylamino)-7-( ~, ~-dibenzylhydrazino)fluoran 3~(dimethylamino)-7-(p-methoxyben2amido)fluoran '$~
r 7-anilino-3-(diethylamino)fluoran 2'-(methylphenylamino)-6l-~methyl-p-tolylamino~fluoran 2'-methyl-6'~cyclohexylaminofluoran 2'-~mino-6'-diethylamino-3'~methylfluoran 2'-amino-6'-diethylaminofluoran 2'-(2-carboxyanilino)-6'-diethylaminofluoran 3-dibenzylamino-7-diethylamino~luoran N-(carboethoxymethyl)aminol-6'-dieth~l~mino~ luar~n 2'-~N-(carboethoxymethyl)-N-methylamino]-6'-diethylamino fluoran ~hodamine lactam N-phenyl Rhodamine lactam Rhodamine anilino lactam 9-p-nitroamino-3,6-bis(diethylamino)~9-Xanthenoyl~
6-benzoic aci~ lactam 9-p-nitroamino-3,6-bis(dimethylamino)-9-thioxantheno~l-6-benzoic acid lactam (2) ~Spiropyrans The following are some o~ the patents which list typical spiropyrans givlng a color when reacted with phenolic materials: Talvakar, U.S. Pate~t No.3,445,2~1; Futaki ek alJ
U.S~ Patent No.3,829,401; Kohmura at al., U.S~ Paten~ No~3,859,112;
Hayashi et al, U.S. Patent Mo.3,773,542; Kimura et alr U.S.
Patent No. 3,666,525; Yahagi et al, Japanese Pat. No.73-63,73~;
Futaki et al, Germany Patent No.2,252,845; Komura et al, German Patent No.2,327,135; Takamizawa et al, Japanese Patent Mo.74-00,069; RobilLard et al, French Patent No.2,204,151; Haino et al, Japanese Patent No.75-01,746; Samat et al, German Patent No.2,522,877; Miyazawa et al, Japanese 75-137,14~;
Takimoto et a:L, Japanese Patent No.75-152,742; Futaki et al, German Patent No.2,252,845; Miya2awa et alr Japanese Patent No.75-137,549.
Typical examples of the spiropyrans llsted in the patents as reacting with phenolic materials to yield colored dyes include-TABLE II
.. .. _ .
6'-chloro-8'-methoxybenzoindolinospiropyran benzothiazolinospiropyran benzo-~ -naphthospiropyran 3-methyl-di- ~-naph~hospiropyran 1,3,3-txime~hyl-6'-chloro~8~~methoxyindoli.nohenzo-spir~opyran 6'chloro-8'-methoxyindolinobenæospiropyran 6-chloro-8~methoxy-1',3',3'~trimethylspixo(1-benzo-pyran-2,2'-indoline) spiro (l-banzopyran-2,2l-naph~hopyran) 8'-methoxybenzoindolinospiropyran 1,3,3-trimethyl-4,7,8'-trimethoxy r (2'H~ benzopyran)-2,2'-indoline]
6-chloro-8'-methyl-1,3,3-trimethylbenzoindolino-spiropyran 2-ethyl-3,3l-spirobinaphthopyran 3-phenyl-di- ~-naphthospiropyran di- ~-naphthospiropyran 3-ethyl-di-~ -napththospiropyran 3,3'-dichlorospirodinaphthopyran 1,3,3-trimethyl~6'-nitrospiro(2'H-l'-benzopyran-2, 2'-indoline) 1,3,3-trimethyl-8'-nitrospiro(2'H-l'-benzopyran-2 r 2'-indoline) 1,3,3-trimethyl-6'-nitro-8'-methoxyspiro(2'~-1'-ben~o-pyran-2,2'-indoline) 1,3,3-trimethyl 5'-nitro-8'-methoxyspirot2'~I-l'-benzo-pyran-2,2'indoline) 3,7 bist3',6'-dimethoxy-9'-spiroxanthyl)pyromellitide _g_ .
Typical examples of phenolic materials listed in the patent literature as reacting with ~he leuco compounds such as the phtalides, naphthal.ides, f luorans, and spiropyrans to form colored dyes include:
.
TP.ELE I I I
4,4'-isopropylidene diphenol 4/4'-isopropylidene-bis~2 methylphenol) 4,4~-isopropylidene-bis~2-phenylph~nol) 4,4'~isopropylidene bis~2-t.butylphenol) 4,4'-sec.butylidene-diphenol 4,4'-sec.but~lidene-bis(2-methylphenol) 4,4'-cyclohexylidene-diphenol 4,4'-cyclohexylidene-bis~2~isopropylphenol) 4/4'-ethylidene-diphenol 2,2'-methylene-bis(5-methylphenoI) 4,4'-ethylidene-bis(2-methylphenol) 4j4'-(1-methylpen~ylidene)diphènol 4,4'-(methylisopentylidene)diphenol 4,4'-~1-methylhexylidene)diphenol 4,4'-(1-ethylbutylidene)diphenol 4,4'-[ethylpropylidene~-bis(2-meth~lphenol) 4,4'-isopropylidenedicatechol 4,4'-benzylidene diphenol 4,4'-isopropylidene-bis(2-chlorophenol) 2,2'-dihydroxydiphenyl 2,2'-methylene-bis(4-chlorophenol) . . ' :
2,2'-methylene-~is(4-methyl-6-t.butylphenol) 4,4'-isopropylidene-bis(2,6-dimethylphenol) 2,2'-thiobis(4,6-dimethylphenol~
4,4'-ethylene diphenol $~
4,4'~ methylbenzylidene)diphenGl 4~t. butylphenol 4-phenylphenol c~ -naphthol ~-naphthol hydroquinone pyrocatechol pyrogallol phloroglucine mO cresol , There are a number of commercial products which use the above-described combinations of leuco dyes and phenolic derivatives. These have fnund applications in thermal copying paper using thermal copie~s. Thermally responsive sheets using these materials have also been used with computer-driven thermal printers~ Sensitized papers containing a combination of leuco dyes and phenolic materials are used in chart recording instruments wherein a colored trace record is o~tained by contacting the paper with a hot pen or stylus. There are certain inherent disadvantages found with the leuco dye-phenolic combinations. Complaints are received on background staining, fading of the record mark, flooding of the image, moisture sensitivity, odor, pressure sensitivity causing accidental marking by paper clips and the like, railroading, and burnout on chart recording papers. Many of the phenolic materials described in the patents are toxic or irritating and cannot be used.
These same leuco dye-phenolic color-forming systems are used in the "carbonless" pressure marking papers and the reactants are kept separate by microencapsulation or by being contained in separate layers. Prsssure contact of these materials results in dye formation. This property is also inherent in the thermal papers and excess pressure will cause accidental markingO Also, for this same reason, the reactants must be ground separately and a solvent or resin binder-solvsnt combination which will dissolve or partially dissolve one or both of the co-reactants will result in premature dye formation in the coating mix. The object of this invention is to eliminate or minimize the problems incured with the leuco dye-phenolic thermal color reacting systems. Another objectlve is to minimize the sublimation or migration of of the phenolic material which has caused problems with staining and change in sensitivity. Still another objective is the manufacture of thermal record sheets with improved image sharpness and definition.
This invention relates to a heat-sensitive recording composition comprising (a) a phenol selected from Table IV of the specification; (b) an amine or an amide; (c) a mixture of heat-sensitive color precursors comprising: (1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a back-ground color of said composition, and (2) R chromogenic compound reactivewith phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic compound being selected Erom the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
This invention further relates to a method for producing a heat-sensitive recording composition comprising the steps of dissolving a binder in a solvent in which complexes of a phenol and a complexing agent selected from the group consisting of amines and amides is insoluble, to form a binder-solvent solution, dispersing in said solution a chromogenic compound reactivewith a phenol at elevated temperatures to develop a color contrasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a back-ground color of said composition; and a hydrogen-bonded molecular complex of a phenol and a complexing agent selected from the group consisting of amines and amides, to form a dispersion, applying said dispersion to a substrate, and evaporating solvent from said dispersion to form a thermo-sensitive coating adapted to develop a color at elevated temperatures.
,~ ,~....
SUMMARY OF THE INVENTION
I have found that the problems and disadvantages of the above described thermal recording systems can be minimized or eliminated by using a combination of leuco dye precursors of the lactone or spiropyran types with cyclic polyketo compounds such as ninhydrin, hydrindantin, isatin, alloxan, and their homologs. I have found that the color precursors may be chemically combined as adducts or chemical complexes of one another which are light in color but can be converted by heat to a dark colored dye. The dye thus formed is not typical of either of the co-reactlng color precursors but rather produces a color additive effect approaching the black dyes most desired for imaging purposes. I have further found that a similar additive effect is obtained when the individual color precursors are mixed together and heated. Presumably, the precursors go through the adduct or complex forming process during fusion and are converted to the final dye by further heating. I have further discovered that molecular complexes of phenolic compounds with amines can be added to the mixtures or adducts of the combined precursors resulting in an increase in dye intensity of the image and also providing faster thermal response at lower temperatures during the imaging process. I have further discovered that certain additives may be used with the color precursor adducts or complexes, -13~
~Q9~33 mixtures of the color precursors, or a combination of these with molecular complexes of phenolics and amines -to further increase the color intensity of the image and also increase the rate of thermal response during imaging.
DETAILED DESCRIPTION OF IN~ENTION
Materials a. Lactones Crystal Violet lactone (3,3-bis-(p-dimethylamino-phenyl)-6-dimethylaminophthalide), Malachite Green lactone (3,3-bis(p-dimethylaminophenyl)phthalide), and 3,3-bis(l-ethyl-2-methylindol-3-yl) phthalide were obtained from the Hilton-Davis Co., Cincinnati, Ohio. The 3,3-bis(p-aminophenyl) phthalide was obtained from the Organic Chemicals Div., Eastman Kodak Co., Rochester, NY.
b. Spiropyrans The indolinospiropyrans were prepared in the normal manner by well known methods described in the art by refluxing e~uimolar amounts of the desired Fischer's base, in these ex-amples 1,3j3-trimethyl-2-methylene indoline or the 5-chloro derivative of the same with the desired aldehyde, e.g., sa-licylaldehyde, 5-nitrosalicylaldehyde, 5-bromo-salicylalde-hyde, 3,5-dibromosalicylaldehyde, and o-vanillin in absolute alcohol for three to four hours, cooling, filtering, and washing the precipitate with alcohol and drying. Similarly, 2-methylbenzothiazolium methyl tosylate was reacted with 2-hydroxy-l-naphthaldehyde and with salicylaldehyde to give the corresponding spiropyrans. The 3-methyl-di-~ -naph~hospiro-pyran was obtained in the usual manner by treating 2-hydroxy-l-naphthaldehyde and methyle~h~l ketone in absolute ethanol i with hydrogen chloride yas and neutralizing the salt formed with sodium carbonate and recrystallizing the product from benzene.
c. Adducts or compLexes of lactones or spiropyrans with cyclic ketones includingninh~drin and isatin.
These were prepared by boiling with stirring for thirty minutes a mixture of 15 parts of lactone or spiropyran and 15 parts of ninhydrin or isatin in 250 parts anhydrous de-natured alcohol. The hot mother liquor was decanted from the residue, chilled in a cold box to crystallize and precipi-tate the adduct, and the precipitated adduct was washed with alcohol and air dried.
d. Complexes The phenolic material is dissolved in anhydrous methanol or ethanol to form a 25 percent solution. The hydro-gen bonding co-reactani amine or amide is added to the alcoholic solution of the phenolic derivative in molecular equivalents corresponding to the number of functional hydroxyl groups in the phenolic compound. For example, two moles of cyclohexyl-amine are added to one mole of a bisphenol, one mole of amine is added to one mole of a mono-hydroxy compound, etc. The mixtures are stirred for a few minutes until they become homo-geneous. In some cases, a solid complex will form and pre-cipitate almost immediately, while others must be chilled in a cold box beforP solid products are obtained. The mixture containing the precipitated complex is then filtered and the precipitate is washed with alcohol and allowed to dry.
The following table contains a number of hydrogen-bonded phenolic complexes which have been prepared in this manner.
I TABLE IV - AROMATIC HYDROXY COMPLEXES
. _ _ _ Phenol AmineDissociation Temp.C
p,p' biphenol ethylene diamine 136-140 " t.butyl amino ethyl methacrylate Bisphenol B ethylenediamine 85-92 " formamide64-66 " t.butyl aminoethyl methacrylate 94-6 4,4'-isopropylidene bis ~2-isopropylphenol) txiethanolamine 60-63 " ethylene diamine100~4 4,4'-isopropylidene bis (2,6-dibromophenol) diethano~l amine107-145 " triethanolami.ne128-157 " ethylene diamine198-215 " diethylenetriamine 210-215 " propylene diamine. 146~156 " formamide 9S~102 " hydrazine 135 150 " t.-butyl aminoethyl methacxy~ate 130-5 4~hydroxy propi.ophenone hydrazine 84-90 2,4-dichloro-6-phenylphenol ethylenediamine 100-4 " diethylenetriamine 115-20 " propylenediamine 92-4 2,2'-methylenebis (3,4,6-trichlorophenol) diethanolamine 75-8 ¦ " triethanolamine 118-23 " ethylenediamine 124-7 " diethylenetriamine 90-110 " propylene diamine125-30 " formamide 125-30 " hydrazine 180 4 t-butylamine ethyl i methacrylate 123-6 2-bromo-4-phenyl phenol ethylenediamine 66-8 " diethylene triamine 78-82 ~ " formamide 55-8 I p-phenyl phenol ethylene diamine137-43 1 " die~hylene triamine 99-104 I " propylene diamine77-81 " formamide 90-5 ¦ " ~ydrazine 145-150 2,2'-thiobis (4,6-dichlorophenol) triethanolamine 120-5 " ethylene diamine125-130 " diethylene triamine 15B-164 " propylene diamine142~5 " ormamide 115-25 " hydra~ine 195-200 4,4'-isopropylidenebis (2,6-dichlorophenol) ethylenediamine 192-5 I " diethylene triamine 210-15 ! propylene diamine170-5 " formamide 100-5 " hydxazine 142-6 I Table IV - Page 2 ! Phenol Amine Disso~iation Temp.C
4,4'isopropylidenebis (2,6-dichlorophenol) t.butyl amine ethyl ~ methacrylate 132-5 ¦ 5-chloro-2-hydroxy benzophenone ethylene diamine 190~4 o-phenylphenol ethylene diamine 55-60 " formamide 50-3 " hydrazine 60-4 Dichlorophene formamide 90-3 2,2'-methylenebis (4-ethyl-6-t.butylphenol) triethanolamine 58-70 Bisphenol A ethylene diamine 100-4 " propylene diamine 94-100 " t.butylamine ethyl methacrylate 90-2 4,4'-thiobis (6-5.butyl-m-cresol) triethanolamine 95-8 " ethylene diamine 106-11 " propylene diamine 125-35 " t.butylamine ethyl methacrylate 62-5 4,4'-butylidenebis ~6-t.butyl-m-cresol) triethanolamine 68-70 2,2'-methylenebis (4-methyl-6-t.butylphenol) diethanolamine 62-5 " ethylene diamine 54-8 p-cyclohexyl phenol triethanolamine 35-40 " ethylene diamine 125-30 " die~hylene triamine 70-85 " propylene diamine 88-90 o-cyclohexyl phenol e~hylene diamine 88-93 " hydrazine 75-80 p-t.butyl phenol ethylene diamine 70-3 ! propylene diamine 54-7 pO-sec. butyl phenol ethylene diamine 50-4 p-bromophenol formamide 35-8 2,4,6-tribromophenol ethylenediamine 135-8 " propylenediamine 85-9 " formamide 90-3 pentachlorophenol diethanolamine 145-55 " triethanolamine 133-7 " ethylenediamine 115-20 " diethylenetriamine 185-90 " propylene diamine 168-72 " formamide 100-5 " hydrazine 200-5 " t.butyl amine ethyl methacrylate 115-20 Phenol Amine Dissociation Temp.C
2,6-dichloroph~nol triethanol~nine g3-6 ethylene diamine110-15 propylenedia~ine100-155 formamide 40-5 hydrazine 115-20 " tobukyl amine ethyl methacrylate 100-5 2-chloro-4-phenyl phenol ethylene diamine130-5 propylene diamine50-4 " hydrazine 108-12 tetrachlorophenol diethanolamine 110-25 triethanolamine 98-10 ethylene diamine165-70 formamide 85-90 hydrazine 163-5 - " t.butyl-amino-ethyl methacrylate 95~100 2,4,6-trichlorophenol ethylene diamine105-14 propylene diamine100~5 formamide 85-90 hydrazine 150-7 t.butyl amine ethyl methacrylate 70-5 ethylenediimino-o-cresol formamide 105-10 tObutylamine ethyl methacrylate 118-12 Bisphenol A benzylamine 70-4 4,4'-isopropylidenebis ~2,6-dibromophenol) 2-amino-1-butanol 155-6~
aminoethylensthanolamine 74-85 2-amino-2-ethyl-1, 3-propenediol 130-40 2-amino-2-methyl-1, 3-propenediol 154-60 aminoethyl piperazine 140-50 2-amino-2-methyl-1-propanol 180-90 2-amino-1-phenyl-1-propanol 100~30 3-amino propanol 190-5 benzylamine 144-8 chloroacetamide114-22 -" 3-chloro-N-methyl acet~nide 80-5 n-decylamine 170-90 1,3-diamino propane 218-225 3-di-n-butyl amino propylamine 150-8 diethanolamine 140-3 diethyl amino ethoxy ethanol 180-5 diethylamino propylamine 175-85 N-diethyl amino propyl 1 methyloctadecylamine 88-100 " diethylisopropanolamine 135-42 j -18-TA~LE IV - Page 4 Phenol Amine Dissociation Temp.C
4,4'-isopropylidenebis (2,6-dibromophenol) diisopropanolamine 65-75 " diisopropylethanolamine 158-165 " dimeth~ylacetamine 95-100 " dimethylamino pxopyl-amine 198-202 " dimethylethanol~mine 135-45 " dimethylformamide 60-5 " M-(l,l-dimethyl-2-hydroxy - ethyl)-2-methyl 1-1,2~
Propane diamine 130-40 " t.-dod~cylaminopro-' pylamine 90-105 ethanoLamine ],70-80 " ~-ethylethanolamine 90-100 " N-ethyldiethanolamine 137-42 " hexamethy,l phosphoramide 127-30 " n-hexylamine 200-10 " triamine 60-80 ! N-2-hydroxyeth methyl dodecylamine 100-11 " N-hydroxyethyl piperazine hydroxy ethyl trihydroxy propyl-ethylene diamine 45-55 iminobispropylamine 210-20 isobutylamine 160-70 " isopropylamine 165-75 " 3-isopropoxypropanol-amine 165-75 " isopropylamine 160-70 " ' methanediamine 140-5 " methyldiethanolamine 132-6 ~ " methyl ethanol amine 143-6 I " N-methyl-bis-amino propyl~mine 210-20 " polyglycol amine H-ll9 115-20 " polyglycolamine II-176195-205 " polyglycolamine H-221 165-174 " 1,2-propanediamine 150-160 " propylenediamine 148-155 " tetramethylethylene-diamine 190-200 " tetramethylguanidine 225-235 " triethanolamine 154-8 " triethylene tetramine 200-15 " triisopropanolamine 135~9 p,p'-biphenol hexamethyl phosphoramide 40-50 4rhydroxy propiophenone hydrazine 84-90 2,2'-methylene bis (2,4,6-trichlorophenol) aminoethylethanolamine165-7 " 2-amino-2-ethyl-1,3-propanediol 151-70 " 2-amino-2-methyl-1,3-propanediol 182-4 " benzylamine 210-16 " t.butylaminoethyl methacrylate 123-6 ~9~
Phenol Amine Dissociation Temp.C
2,2'-methylene bis (2,4,6 trichlorophenol) diethanolamine 75-8 Il diethylenetriamine 90-110 2,2'-methylene bis (2, 4,6-trichlorophenol) dimethylethanolamine 183-93 N-ethyldiethanolamine 124-7 ethylene diamine 187-92 " formamide 125-30 " hexamethyl phosphoxamide 85-90 " hydrazine 180-~
" N-methylbisam.ino propylamine 157-55 " methyldiethanolamine 154-7 2~2'-methylsne bis (2, 4,6-trichlorophenol) methyle~hanolamine 193-200 " polyglycolamine H-176 208-24 " propylenediamine 135-40 " triethanolamine 142-6 2,4-dichloro-6-phenyl phenol diethylen0 triamine 115-20 " ethylene diamine 100-4 " propylenediamine 92-4 2-bromo-4-phenyl phenol benzylamine 85-95 diethylenetriamine 78-82 " ethylenediamine 66-8 " formamide 55-~
" hydrazine 82-8 p-phenyl phenol benzylamine 70 " diethlenetriamine 99-104 ethylenediamine 137-43 " formamide 113-5 " hexamethyl phosphoramide 34-5 " hydrazine lSS-8 " propylene diamine 71-81 " triethylene tetramine 63-5 2,2'-thiobis (4,6-dichlorophenol) 2-amino-2-ethyl-1, 3-propanediol 125-59 " benzylamine 197-9 diethanolamine 143-7 " diethylene triamine 158-74 " diiosopropanolamine 155-62 " dimethylacetamide 190-3 dimethylethanol amine 120 3 N-ethyldiethanolamine 127-30 " ethylene diamine 125-30 " hydrazine 195-200 iminobispropylamine 50-74 methyldiethanolamine 127-40 . polyglycolamine 210-14 propylene diamine 142-S
" formamide 115-25 triethanolamine 165-8 " triisopropanolamine 151-S
2,2' methylene bis (4-chlorophenol) benzylamine 60-100 Phenol Amine Dissociation 2,2' methylene bis ~4- Temp.C
chlorophenol) formamide 90-3 4,4'-isopropylidene bis (2,6-dichloxophenol~ 2-amino-1-butanol 166-70 " ami.noethylethanolamine 154-8 2-amino-2-ethyl-1,2-propanediol 166-8 2-amino-2-methyl-1~3-propanediol 172-5 3-amino propanol 180-90 amylamine 200-10 " aniline 90-6 " benzylamine 145-55 " t~butylaminoethyl methacrylate 132-5 " cyclohexylamine 190-204 j " n-decylamine 193-8 I " 1,3-diamino propane 230~5 dibutylamine 124-57 3-di-n-butylamine propylamine 155-64 dibutylmethylamine 120-31 " dicyclohexylamine 202-6 diethanolamine 150-3 " diethylamine . 142-7 " diethylaminoethyl methacrylate 115-7 " ~ -diethylaminopro-pionitrile 94-6 " 3-ethylamino propioni-trile 103-5 di-2-ethylhexylamine 100-5 diethylene triamine 210-15 diethylisopropanolamine 125-35 diisopropylethanolamine 162-4 " diisopropyla~ine 141-52 ~ -dimethylamino propio-nitrile 70-3 " dimethylaminopropyl-amine 197-2Q3 dimethylethanolamine140-6 di-n-propylamine 142-53 3-t.-dodecylaminopropy-lamine lG0-5 ethanolamine 96~104 N-ethylcyclohexylamine 161-78 N-ethyldiethanolamine 154-5 ethylene diamine 208-10 N-ethylethanolamine 87-110 formamide 103-8 hexamethylphosphoramide 122-4 n-hexylamine 168-85 hydrazine . 142-6 hydroxyethylethylene diamine 94-100 iminobispropylamine 220-3 isobutylamine 152-67 isodecylamine 187-95 Phenol ~mine Dissociation 4,4'-isopropylidene bis Temp.C
¦ (2,6-dichlorophenol) isooctylamine 172-~4 isopropanolamine150-7 3-isopropoxyisopropanol-amine 160~7 ~ -isopropylaminopr~
pionitrile 103-7 3-isopropylamine pro-pyl~mine 122-7 isoquinoline 102-4 2,6-lutidi~e 125-32 methanediamine 186-90 N-]methyl bis amino propylamine 219-36 methylaminopropylamine 207-13 methylbenzyla~ine 145~55 N-methyldiethanolamine 148-52 N-methylethanolamine ~5-102 3,3'-methyl iminobis propylamine 190-9 N-methyl morpholine 120-4 N-methyl-2-pyrrolidone 70-3 morpholine 159-60 phenyldiethanolamine 85-95 phenylethanolamine 88 95 2,2'-phenyliminodiethano-lamine 55-70 ~ -picoline 96-9 polyglycolamine H-ll9 156-63 polyglycolamine H-169 123-33 polyglycolamine H-176 210-18 polyglycolamine H-221196-200 propylenedi~mine 168-75 pyridine 117-30 tetraethylene pentamine 92-102 tributylamine . 103-8 triethylamine 155-64 triethanolamine 139-45 triethylene tetramine215-20 triisopropanolamine 125-30 trimethylenediamine 230-5 dimethylacetamide 132
r 7-anilino-3-(diethylamino)fluoran 2'-(methylphenylamino)-6l-~methyl-p-tolylamino~fluoran 2'-methyl-6'~cyclohexylaminofluoran 2'-~mino-6'-diethylamino-3'~methylfluoran 2'-amino-6'-diethylaminofluoran 2'-(2-carboxyanilino)-6'-diethylaminofluoran 3-dibenzylamino-7-diethylamino~luoran N-(carboethoxymethyl)aminol-6'-dieth~l~mino~ luar~n 2'-~N-(carboethoxymethyl)-N-methylamino]-6'-diethylamino fluoran ~hodamine lactam N-phenyl Rhodamine lactam Rhodamine anilino lactam 9-p-nitroamino-3,6-bis(diethylamino)~9-Xanthenoyl~
6-benzoic aci~ lactam 9-p-nitroamino-3,6-bis(dimethylamino)-9-thioxantheno~l-6-benzoic acid lactam (2) ~Spiropyrans The following are some o~ the patents which list typical spiropyrans givlng a color when reacted with phenolic materials: Talvakar, U.S. Pate~t No.3,445,2~1; Futaki ek alJ
U.S~ Patent No.3,829,401; Kohmura at al., U.S~ Paten~ No~3,859,112;
Hayashi et al, U.S. Patent Mo.3,773,542; Kimura et alr U.S.
Patent No. 3,666,525; Yahagi et al, Japanese Pat. No.73-63,73~;
Futaki et al, Germany Patent No.2,252,845; Komura et al, German Patent No.2,327,135; Takamizawa et al, Japanese Patent Mo.74-00,069; RobilLard et al, French Patent No.2,204,151; Haino et al, Japanese Patent No.75-01,746; Samat et al, German Patent No.2,522,877; Miyazawa et al, Japanese 75-137,14~;
Takimoto et a:L, Japanese Patent No.75-152,742; Futaki et al, German Patent No.2,252,845; Miya2awa et alr Japanese Patent No.75-137,549.
Typical examples of the spiropyrans llsted in the patents as reacting with phenolic materials to yield colored dyes include-TABLE II
.. .. _ .
6'-chloro-8'-methoxybenzoindolinospiropyran benzothiazolinospiropyran benzo-~ -naphthospiropyran 3-methyl-di- ~-naph~hospiropyran 1,3,3-txime~hyl-6'-chloro~8~~methoxyindoli.nohenzo-spir~opyran 6'chloro-8'-methoxyindolinobenæospiropyran 6-chloro-8~methoxy-1',3',3'~trimethylspixo(1-benzo-pyran-2,2'-indoline) spiro (l-banzopyran-2,2l-naph~hopyran) 8'-methoxybenzoindolinospiropyran 1,3,3-trimethyl-4,7,8'-trimethoxy r (2'H~ benzopyran)-2,2'-indoline]
6-chloro-8'-methyl-1,3,3-trimethylbenzoindolino-spiropyran 2-ethyl-3,3l-spirobinaphthopyran 3-phenyl-di- ~-naphthospiropyran di- ~-naphthospiropyran 3-ethyl-di-~ -napththospiropyran 3,3'-dichlorospirodinaphthopyran 1,3,3-trimethyl~6'-nitrospiro(2'H-l'-benzopyran-2, 2'-indoline) 1,3,3-trimethyl-8'-nitrospiro(2'H-l'-benzopyran-2 r 2'-indoline) 1,3,3-trimethyl-6'-nitro-8'-methoxyspiro(2'~-1'-ben~o-pyran-2,2'-indoline) 1,3,3-trimethyl 5'-nitro-8'-methoxyspirot2'~I-l'-benzo-pyran-2,2'indoline) 3,7 bist3',6'-dimethoxy-9'-spiroxanthyl)pyromellitide _g_ .
Typical examples of phenolic materials listed in the patent literature as reacting with ~he leuco compounds such as the phtalides, naphthal.ides, f luorans, and spiropyrans to form colored dyes include:
.
TP.ELE I I I
4,4'-isopropylidene diphenol 4/4'-isopropylidene-bis~2 methylphenol) 4,4~-isopropylidene-bis~2-phenylph~nol) 4,4'~isopropylidene bis~2-t.butylphenol) 4,4'-sec.butylidene-diphenol 4,4'-sec.but~lidene-bis(2-methylphenol) 4,4'-cyclohexylidene-diphenol 4,4'-cyclohexylidene-bis~2~isopropylphenol) 4/4'-ethylidene-diphenol 2,2'-methylene-bis(5-methylphenoI) 4,4'-ethylidene-bis(2-methylphenol) 4j4'-(1-methylpen~ylidene)diphènol 4,4'-(methylisopentylidene)diphenol 4,4'-~1-methylhexylidene)diphenol 4,4'-(1-ethylbutylidene)diphenol 4,4'-[ethylpropylidene~-bis(2-meth~lphenol) 4,4'-isopropylidenedicatechol 4,4'-benzylidene diphenol 4,4'-isopropylidene-bis(2-chlorophenol) 2,2'-dihydroxydiphenyl 2,2'-methylene-bis(4-chlorophenol) . . ' :
2,2'-methylene-~is(4-methyl-6-t.butylphenol) 4,4'-isopropylidene-bis(2,6-dimethylphenol) 2,2'-thiobis(4,6-dimethylphenol~
4,4'-ethylene diphenol $~
4,4'~ methylbenzylidene)diphenGl 4~t. butylphenol 4-phenylphenol c~ -naphthol ~-naphthol hydroquinone pyrocatechol pyrogallol phloroglucine mO cresol , There are a number of commercial products which use the above-described combinations of leuco dyes and phenolic derivatives. These have fnund applications in thermal copying paper using thermal copie~s. Thermally responsive sheets using these materials have also been used with computer-driven thermal printers~ Sensitized papers containing a combination of leuco dyes and phenolic materials are used in chart recording instruments wherein a colored trace record is o~tained by contacting the paper with a hot pen or stylus. There are certain inherent disadvantages found with the leuco dye-phenolic combinations. Complaints are received on background staining, fading of the record mark, flooding of the image, moisture sensitivity, odor, pressure sensitivity causing accidental marking by paper clips and the like, railroading, and burnout on chart recording papers. Many of the phenolic materials described in the patents are toxic or irritating and cannot be used.
These same leuco dye-phenolic color-forming systems are used in the "carbonless" pressure marking papers and the reactants are kept separate by microencapsulation or by being contained in separate layers. Prsssure contact of these materials results in dye formation. This property is also inherent in the thermal papers and excess pressure will cause accidental markingO Also, for this same reason, the reactants must be ground separately and a solvent or resin binder-solvsnt combination which will dissolve or partially dissolve one or both of the co-reactants will result in premature dye formation in the coating mix. The object of this invention is to eliminate or minimize the problems incured with the leuco dye-phenolic thermal color reacting systems. Another objectlve is to minimize the sublimation or migration of of the phenolic material which has caused problems with staining and change in sensitivity. Still another objective is the manufacture of thermal record sheets with improved image sharpness and definition.
This invention relates to a heat-sensitive recording composition comprising (a) a phenol selected from Table IV of the specification; (b) an amine or an amide; (c) a mixture of heat-sensitive color precursors comprising: (1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a back-ground color of said composition, and (2) R chromogenic compound reactivewith phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic compound being selected Erom the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
This invention further relates to a method for producing a heat-sensitive recording composition comprising the steps of dissolving a binder in a solvent in which complexes of a phenol and a complexing agent selected from the group consisting of amines and amides is insoluble, to form a binder-solvent solution, dispersing in said solution a chromogenic compound reactivewith a phenol at elevated temperatures to develop a color contrasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a back-ground color of said composition; and a hydrogen-bonded molecular complex of a phenol and a complexing agent selected from the group consisting of amines and amides, to form a dispersion, applying said dispersion to a substrate, and evaporating solvent from said dispersion to form a thermo-sensitive coating adapted to develop a color at elevated temperatures.
,~ ,~....
SUMMARY OF THE INVENTION
I have found that the problems and disadvantages of the above described thermal recording systems can be minimized or eliminated by using a combination of leuco dye precursors of the lactone or spiropyran types with cyclic polyketo compounds such as ninhydrin, hydrindantin, isatin, alloxan, and their homologs. I have found that the color precursors may be chemically combined as adducts or chemical complexes of one another which are light in color but can be converted by heat to a dark colored dye. The dye thus formed is not typical of either of the co-reactlng color precursors but rather produces a color additive effect approaching the black dyes most desired for imaging purposes. I have further found that a similar additive effect is obtained when the individual color precursors are mixed together and heated. Presumably, the precursors go through the adduct or complex forming process during fusion and are converted to the final dye by further heating. I have further discovered that molecular complexes of phenolic compounds with amines can be added to the mixtures or adducts of the combined precursors resulting in an increase in dye intensity of the image and also providing faster thermal response at lower temperatures during the imaging process. I have further discovered that certain additives may be used with the color precursor adducts or complexes, -13~
~Q9~33 mixtures of the color precursors, or a combination of these with molecular complexes of phenolics and amines -to further increase the color intensity of the image and also increase the rate of thermal response during imaging.
DETAILED DESCRIPTION OF IN~ENTION
Materials a. Lactones Crystal Violet lactone (3,3-bis-(p-dimethylamino-phenyl)-6-dimethylaminophthalide), Malachite Green lactone (3,3-bis(p-dimethylaminophenyl)phthalide), and 3,3-bis(l-ethyl-2-methylindol-3-yl) phthalide were obtained from the Hilton-Davis Co., Cincinnati, Ohio. The 3,3-bis(p-aminophenyl) phthalide was obtained from the Organic Chemicals Div., Eastman Kodak Co., Rochester, NY.
b. Spiropyrans The indolinospiropyrans were prepared in the normal manner by well known methods described in the art by refluxing e~uimolar amounts of the desired Fischer's base, in these ex-amples 1,3j3-trimethyl-2-methylene indoline or the 5-chloro derivative of the same with the desired aldehyde, e.g., sa-licylaldehyde, 5-nitrosalicylaldehyde, 5-bromo-salicylalde-hyde, 3,5-dibromosalicylaldehyde, and o-vanillin in absolute alcohol for three to four hours, cooling, filtering, and washing the precipitate with alcohol and drying. Similarly, 2-methylbenzothiazolium methyl tosylate was reacted with 2-hydroxy-l-naphthaldehyde and with salicylaldehyde to give the corresponding spiropyrans. The 3-methyl-di-~ -naph~hospiro-pyran was obtained in the usual manner by treating 2-hydroxy-l-naphthaldehyde and methyle~h~l ketone in absolute ethanol i with hydrogen chloride yas and neutralizing the salt formed with sodium carbonate and recrystallizing the product from benzene.
c. Adducts or compLexes of lactones or spiropyrans with cyclic ketones includingninh~drin and isatin.
These were prepared by boiling with stirring for thirty minutes a mixture of 15 parts of lactone or spiropyran and 15 parts of ninhydrin or isatin in 250 parts anhydrous de-natured alcohol. The hot mother liquor was decanted from the residue, chilled in a cold box to crystallize and precipi-tate the adduct, and the precipitated adduct was washed with alcohol and air dried.
d. Complexes The phenolic material is dissolved in anhydrous methanol or ethanol to form a 25 percent solution. The hydro-gen bonding co-reactani amine or amide is added to the alcoholic solution of the phenolic derivative in molecular equivalents corresponding to the number of functional hydroxyl groups in the phenolic compound. For example, two moles of cyclohexyl-amine are added to one mole of a bisphenol, one mole of amine is added to one mole of a mono-hydroxy compound, etc. The mixtures are stirred for a few minutes until they become homo-geneous. In some cases, a solid complex will form and pre-cipitate almost immediately, while others must be chilled in a cold box beforP solid products are obtained. The mixture containing the precipitated complex is then filtered and the precipitate is washed with alcohol and allowed to dry.
The following table contains a number of hydrogen-bonded phenolic complexes which have been prepared in this manner.
I TABLE IV - AROMATIC HYDROXY COMPLEXES
. _ _ _ Phenol AmineDissociation Temp.C
p,p' biphenol ethylene diamine 136-140 " t.butyl amino ethyl methacrylate Bisphenol B ethylenediamine 85-92 " formamide64-66 " t.butyl aminoethyl methacrylate 94-6 4,4'-isopropylidene bis ~2-isopropylphenol) txiethanolamine 60-63 " ethylene diamine100~4 4,4'-isopropylidene bis (2,6-dibromophenol) diethano~l amine107-145 " triethanolami.ne128-157 " ethylene diamine198-215 " diethylenetriamine 210-215 " propylene diamine. 146~156 " formamide 9S~102 " hydrazine 135 150 " t.-butyl aminoethyl methacxy~ate 130-5 4~hydroxy propi.ophenone hydrazine 84-90 2,4-dichloro-6-phenylphenol ethylenediamine 100-4 " diethylenetriamine 115-20 " propylenediamine 92-4 2,2'-methylenebis (3,4,6-trichlorophenol) diethanolamine 75-8 ¦ " triethanolamine 118-23 " ethylenediamine 124-7 " diethylenetriamine 90-110 " propylene diamine125-30 " formamide 125-30 " hydrazine 180 4 t-butylamine ethyl i methacrylate 123-6 2-bromo-4-phenyl phenol ethylenediamine 66-8 " diethylene triamine 78-82 ~ " formamide 55-8 I p-phenyl phenol ethylene diamine137-43 1 " die~hylene triamine 99-104 I " propylene diamine77-81 " formamide 90-5 ¦ " ~ydrazine 145-150 2,2'-thiobis (4,6-dichlorophenol) triethanolamine 120-5 " ethylene diamine125-130 " diethylene triamine 15B-164 " propylene diamine142~5 " ormamide 115-25 " hydra~ine 195-200 4,4'-isopropylidenebis (2,6-dichlorophenol) ethylenediamine 192-5 I " diethylene triamine 210-15 ! propylene diamine170-5 " formamide 100-5 " hydxazine 142-6 I Table IV - Page 2 ! Phenol Amine Disso~iation Temp.C
4,4'isopropylidenebis (2,6-dichlorophenol) t.butyl amine ethyl ~ methacrylate 132-5 ¦ 5-chloro-2-hydroxy benzophenone ethylene diamine 190~4 o-phenylphenol ethylene diamine 55-60 " formamide 50-3 " hydrazine 60-4 Dichlorophene formamide 90-3 2,2'-methylenebis (4-ethyl-6-t.butylphenol) triethanolamine 58-70 Bisphenol A ethylene diamine 100-4 " propylene diamine 94-100 " t.butylamine ethyl methacrylate 90-2 4,4'-thiobis (6-5.butyl-m-cresol) triethanolamine 95-8 " ethylene diamine 106-11 " propylene diamine 125-35 " t.butylamine ethyl methacrylate 62-5 4,4'-butylidenebis ~6-t.butyl-m-cresol) triethanolamine 68-70 2,2'-methylenebis (4-methyl-6-t.butylphenol) diethanolamine 62-5 " ethylene diamine 54-8 p-cyclohexyl phenol triethanolamine 35-40 " ethylene diamine 125-30 " die~hylene triamine 70-85 " propylene diamine 88-90 o-cyclohexyl phenol e~hylene diamine 88-93 " hydrazine 75-80 p-t.butyl phenol ethylene diamine 70-3 ! propylene diamine 54-7 pO-sec. butyl phenol ethylene diamine 50-4 p-bromophenol formamide 35-8 2,4,6-tribromophenol ethylenediamine 135-8 " propylenediamine 85-9 " formamide 90-3 pentachlorophenol diethanolamine 145-55 " triethanolamine 133-7 " ethylenediamine 115-20 " diethylenetriamine 185-90 " propylene diamine 168-72 " formamide 100-5 " hydrazine 200-5 " t.butyl amine ethyl methacrylate 115-20 Phenol Amine Dissociation Temp.C
2,6-dichloroph~nol triethanol~nine g3-6 ethylene diamine110-15 propylenedia~ine100-155 formamide 40-5 hydrazine 115-20 " tobukyl amine ethyl methacrylate 100-5 2-chloro-4-phenyl phenol ethylene diamine130-5 propylene diamine50-4 " hydrazine 108-12 tetrachlorophenol diethanolamine 110-25 triethanolamine 98-10 ethylene diamine165-70 formamide 85-90 hydrazine 163-5 - " t.butyl-amino-ethyl methacrylate 95~100 2,4,6-trichlorophenol ethylene diamine105-14 propylene diamine100~5 formamide 85-90 hydrazine 150-7 t.butyl amine ethyl methacrylate 70-5 ethylenediimino-o-cresol formamide 105-10 tObutylamine ethyl methacrylate 118-12 Bisphenol A benzylamine 70-4 4,4'-isopropylidenebis ~2,6-dibromophenol) 2-amino-1-butanol 155-6~
aminoethylensthanolamine 74-85 2-amino-2-ethyl-1, 3-propenediol 130-40 2-amino-2-methyl-1, 3-propenediol 154-60 aminoethyl piperazine 140-50 2-amino-2-methyl-1-propanol 180-90 2-amino-1-phenyl-1-propanol 100~30 3-amino propanol 190-5 benzylamine 144-8 chloroacetamide114-22 -" 3-chloro-N-methyl acet~nide 80-5 n-decylamine 170-90 1,3-diamino propane 218-225 3-di-n-butyl amino propylamine 150-8 diethanolamine 140-3 diethyl amino ethoxy ethanol 180-5 diethylamino propylamine 175-85 N-diethyl amino propyl 1 methyloctadecylamine 88-100 " diethylisopropanolamine 135-42 j -18-TA~LE IV - Page 4 Phenol Amine Dissociation Temp.C
4,4'-isopropylidenebis (2,6-dibromophenol) diisopropanolamine 65-75 " diisopropylethanolamine 158-165 " dimeth~ylacetamine 95-100 " dimethylamino pxopyl-amine 198-202 " dimethylethanol~mine 135-45 " dimethylformamide 60-5 " M-(l,l-dimethyl-2-hydroxy - ethyl)-2-methyl 1-1,2~
Propane diamine 130-40 " t.-dod~cylaminopro-' pylamine 90-105 ethanoLamine ],70-80 " ~-ethylethanolamine 90-100 " N-ethyldiethanolamine 137-42 " hexamethy,l phosphoramide 127-30 " n-hexylamine 200-10 " triamine 60-80 ! N-2-hydroxyeth methyl dodecylamine 100-11 " N-hydroxyethyl piperazine hydroxy ethyl trihydroxy propyl-ethylene diamine 45-55 iminobispropylamine 210-20 isobutylamine 160-70 " isopropylamine 165-75 " 3-isopropoxypropanol-amine 165-75 " isopropylamine 160-70 " ' methanediamine 140-5 " methyldiethanolamine 132-6 ~ " methyl ethanol amine 143-6 I " N-methyl-bis-amino propyl~mine 210-20 " polyglycol amine H-ll9 115-20 " polyglycolamine II-176195-205 " polyglycolamine H-221 165-174 " 1,2-propanediamine 150-160 " propylenediamine 148-155 " tetramethylethylene-diamine 190-200 " tetramethylguanidine 225-235 " triethanolamine 154-8 " triethylene tetramine 200-15 " triisopropanolamine 135~9 p,p'-biphenol hexamethyl phosphoramide 40-50 4rhydroxy propiophenone hydrazine 84-90 2,2'-methylene bis (2,4,6-trichlorophenol) aminoethylethanolamine165-7 " 2-amino-2-ethyl-1,3-propanediol 151-70 " 2-amino-2-methyl-1,3-propanediol 182-4 " benzylamine 210-16 " t.butylaminoethyl methacrylate 123-6 ~9~
Phenol Amine Dissociation Temp.C
2,2'-methylene bis (2,4,6 trichlorophenol) diethanolamine 75-8 Il diethylenetriamine 90-110 2,2'-methylene bis (2, 4,6-trichlorophenol) dimethylethanolamine 183-93 N-ethyldiethanolamine 124-7 ethylene diamine 187-92 " formamide 125-30 " hexamethyl phosphoxamide 85-90 " hydrazine 180-~
" N-methylbisam.ino propylamine 157-55 " methyldiethanolamine 154-7 2~2'-methylsne bis (2, 4,6-trichlorophenol) methyle~hanolamine 193-200 " polyglycolamine H-176 208-24 " propylenediamine 135-40 " triethanolamine 142-6 2,4-dichloro-6-phenyl phenol diethylen0 triamine 115-20 " ethylene diamine 100-4 " propylenediamine 92-4 2-bromo-4-phenyl phenol benzylamine 85-95 diethylenetriamine 78-82 " ethylenediamine 66-8 " formamide 55-~
" hydrazine 82-8 p-phenyl phenol benzylamine 70 " diethlenetriamine 99-104 ethylenediamine 137-43 " formamide 113-5 " hexamethyl phosphoramide 34-5 " hydrazine lSS-8 " propylene diamine 71-81 " triethylene tetramine 63-5 2,2'-thiobis (4,6-dichlorophenol) 2-amino-2-ethyl-1, 3-propanediol 125-59 " benzylamine 197-9 diethanolamine 143-7 " diethylene triamine 158-74 " diiosopropanolamine 155-62 " dimethylacetamide 190-3 dimethylethanol amine 120 3 N-ethyldiethanolamine 127-30 " ethylene diamine 125-30 " hydrazine 195-200 iminobispropylamine 50-74 methyldiethanolamine 127-40 . polyglycolamine 210-14 propylene diamine 142-S
" formamide 115-25 triethanolamine 165-8 " triisopropanolamine 151-S
2,2' methylene bis (4-chlorophenol) benzylamine 60-100 Phenol Amine Dissociation 2,2' methylene bis ~4- Temp.C
chlorophenol) formamide 90-3 4,4'-isopropylidene bis (2,6-dichloxophenol~ 2-amino-1-butanol 166-70 " ami.noethylethanolamine 154-8 2-amino-2-ethyl-1,2-propanediol 166-8 2-amino-2-methyl-1~3-propanediol 172-5 3-amino propanol 180-90 amylamine 200-10 " aniline 90-6 " benzylamine 145-55 " t~butylaminoethyl methacrylate 132-5 " cyclohexylamine 190-204 j " n-decylamine 193-8 I " 1,3-diamino propane 230~5 dibutylamine 124-57 3-di-n-butylamine propylamine 155-64 dibutylmethylamine 120-31 " dicyclohexylamine 202-6 diethanolamine 150-3 " diethylamine . 142-7 " diethylaminoethyl methacrylate 115-7 " ~ -diethylaminopro-pionitrile 94-6 " 3-ethylamino propioni-trile 103-5 di-2-ethylhexylamine 100-5 diethylene triamine 210-15 diethylisopropanolamine 125-35 diisopropylethanolamine 162-4 " diisopropyla~ine 141-52 ~ -dimethylamino propio-nitrile 70-3 " dimethylaminopropyl-amine 197-2Q3 dimethylethanolamine140-6 di-n-propylamine 142-53 3-t.-dodecylaminopropy-lamine lG0-5 ethanolamine 96~104 N-ethylcyclohexylamine 161-78 N-ethyldiethanolamine 154-5 ethylene diamine 208-10 N-ethylethanolamine 87-110 formamide 103-8 hexamethylphosphoramide 122-4 n-hexylamine 168-85 hydrazine . 142-6 hydroxyethylethylene diamine 94-100 iminobispropylamine 220-3 isobutylamine 152-67 isodecylamine 187-95 Phenol ~mine Dissociation 4,4'-isopropylidene bis Temp.C
¦ (2,6-dichlorophenol) isooctylamine 172-~4 isopropanolamine150-7 3-isopropoxyisopropanol-amine 160~7 ~ -isopropylaminopr~
pionitrile 103-7 3-isopropylamine pro-pyl~mine 122-7 isoquinoline 102-4 2,6-lutidi~e 125-32 methanediamine 186-90 N-]methyl bis amino propylamine 219-36 methylaminopropylamine 207-13 methylbenzyla~ine 145~55 N-methyldiethanolamine 148-52 N-methylethanolamine ~5-102 3,3'-methyl iminobis propylamine 190-9 N-methyl morpholine 120-4 N-methyl-2-pyrrolidone 70-3 morpholine 159-60 phenyldiethanolamine 85-95 phenylethanolamine 88 95 2,2'-phenyliminodiethano-lamine 55-70 ~ -picoline 96-9 polyglycolamine H-ll9 156-63 polyglycolamine H-169 123-33 polyglycolamine H-176 210-18 polyglycolamine H-221196-200 propylenedi~mine 168-75 pyridine 117-30 tetraethylene pentamine 92-102 tributylamine . 103-8 triethylamine 155-64 triethanolamine 139-45 triethylene tetramine215-20 triisopropanolamine 125-30 trimethylenediamine 230-5 dimethylacetamide 132
5-cloro-2-hydroxy benzo-phenone ethylenediamine 190-4 2,2'-methylene bis (4-ethyl
6~dibutyl phenol) benzylamine . 76-85 triethanolamine ~8-70 o-phenyl phenol ethylenediamine S5-60 formamide 50-3 hydra2ine 60-4 4,4'-isopropyl:idene bis-phenol benzylamine 80-90 t.butylaminoethyl methacrylate 30-2 cyclohexylamine 108-10 dibutylamine 120-52 diethylamine 117-53 dimethylamine propylamine 105-8 .
Dissociation Phenol ~mi~e 4,4'-isopropylidene bis-phenol di-n-propylamine 90-100 ethylenediamine 100-4 formamide 66 8 isobutylamine 88-93 methanediamine 128-30 N-methyliminobis~
propylamine 94-8 propylenediamin0 95-100 triethylenetetramine137-~
4,4'-thiobis (6-t.butyl-- m-cresol) t.butylamino~:ethyl methacrylate 62~5 cyclohexylamine 78-85 ethylenediamine 112-15 iminobispropylamine85~95 isopropylamine 164-6 propylenediamine 130-6 pyridine 160-5 triethanolamine 95-8 4,4'-butylidene bis (m-cresol) acatamine 82-3 benzylamine 135 cyclohexylamine 214-7 ethylenediamine 213-7 triethanolamin~ 68-70 2,2'-methylene bis (4-methyl-6-~.butylphenol) 2-amino-1-butanol 58-64 benzylamine 69-79 decylamine 52-3 1,3-diaminopropane 50-5 N-dibutylethylamine 60-5 diethanolamine 62-5 di-n-hexylamine 81-9 ethylcyclohexylamine92-4 N-ethyl diethanolamine 68-71 isopropylaminoiso-propylamine 128-32 ethylene diamine 54-8 hexamethyl phosphoramide 58-65 isoquinoline 121-5 N-methyldiethanolamine 127-34 methyl ethanolamine74-84 triamylamine 65-75 triethanolamine 61-5 p-cyclohexyl phenol triethanolamine 35 40 benzylamine 50-5 diethylenetriamine 70-85 ethylene diamine 125-30 hexamethyl phosphoramide 97-109 hydrazine 115-20 propylene diamine 88-90 o-cyclohexyl phenol benxylamine 82-95 ethylene diamine 88-93 hydrazine 75-80 ~0 TABLE IV - Pa~e 9 Dlssociation Phenol Amine Temp.C
p.t-butyl phenol benzylamine 70-80 ~thylenedi~mine70-3 " hydrazine 45-50 " propylenediamine 54-6 p-bromophenol formamide 35-8 2,4-dibromophenol benzylamine 80-5 2,4,6-tribromophenol t.butyl amin~ ethyl methacrylate 68-71 " benzylamine 125-30 " ethylene diamine 135-8 formamide 90-3 " hydrazine 145-54 " propylene diamine 87-92 Pentachlorophenol benzylamine 155-60 t.-butylaminoethyl methacrylate 115-20 diethanolamine145-55 " diethylenetriamine 185-90 " ethylenediamine115-20 " formamide 100-105 hexamethyl phosphoramide 79-83 " hydrazine ?00-205 propylenediamine 168-72 " triethanolamine133-7 2,6-dichlorophenol benzylamine 100-5 t.butylaminoethyl methacrylate 100-5 diethanolamine 83-6 " ethylenediamine110-15 " formamide 40-5 " hydrazine 115-20 " propylenediamine 115-25 2-chloro-4-phenyl phenol benzylamine 95-100 " ethylenedi~mine130-5 " hydrazine 108-12 " propylenediamine 50-4 tetrachlorophenol benzylamine 115-25 " t.butylaminoethyl methacrylate 95-100 " diethanolamine110-25 " ethylenediamine192-5 " formamide 85~90 " hydra2ine 163-5 " propylenediamine 165-70 " triethanolamine98-104 2,4,6-trichlorophenol benzylamine 120-5 " ~.bu~ylaminoethyl methacrylate 70-5 " ethylenediamine105-14 formamide 85-~0 hydrazine 150-7 " propylenediamine 100-5 2,4-dichloro-1-naphthol benæylamine 55-60 " diethanolamine65-70 ~9~
Dissociation Phenol Amine _Temp.C
2,4-dichloro-1-naphthol diethylenetriamine 79-83 formamide 78-82 hydrazine 83~93 2-naph`thol triethanolamine 63-5 " benzylamine 40-5 " ethylenediamine 86-9 formamide 56-59 " hydrazine llO-lZ
4,4-isopropylidene bis (p-chlorophenol) benzylamine 105-10 formamide 55-60 hexamethyl phosphvramide 46-8 hydrazine 100-112 2,6-dibromo-t.butyl phenol benzylamine 75-80 diethylenetriamine85-96 " ethylenediamine95-105 hydraxine 105-110 propylenediamine95-100 " triethanolamine104-6 p-phenoxy phenol ethylenediamine56-62 " hydraxine 48-56 2,4,5-trichlorophenol benezylamine 118-20 " t.butylaminoethyl methacrylate 55 60 diethanolamine 105-10 " diethylenetriamine 85-95 " ethylenediamine55-60 " - hydrazine 94-100 " propylenediamine96-104 l,l-di (4-hydroxyphenyl) cyclohexane diethanolamine100-112 " propylenediamine120-5 l,l-di (3,5-dibromo-4-hydroxy phenyl) cyclohexane diethanola~ine 149-54 " propylenediamine175-80 3,3-bis ~3,5-dibromo-4-hydroxy phenyl) pentane propylenediamine 183-g2 2,2-bis (3,.5-dibr~mo-4-hydroxy phenyl) pentane diethanolamine 110-18 " propylenediamine180-90 bis (3,5-dibromo-4-hydroxy phenyl) methane diethanolamine 115-23 2,2-bis ~3,5-dibromo-4-hydroxy phenyl) butane diethanolamine 142-5 " propylenediamine174-6 3,3'-5,5'-tetrabromo-4,4'-dihydroxy biphenyl diethanolamine 173-80 l-phenyl-l, l-di (3,5-di-bromo-4-hydroxy phenyl) ethane diethanolamine 145-50 " propylenediamine . 185-200 2,2-di (3,5-dibromo-4-hydroxypheny].) 4-methyl-penetane diethanolamine 115-20 " propylenediamine190-4 T~BLE IV ~ Page 11 Dissociation Phenol Amine Tem .~C
P _ ._ 2,2-di (3,5 di~romo-4~
hydroxy phenyl) heptane diethanolamine 145-50 " prop~ylenediamine 195-7 l,l-di (3,5-dibromo-4-hydroxy phenyl) butane diethanolamine 100-15 " propylene diamine 173-7 2,2-di (3,5-dibromo-4-hydroxy phenyl) octane diet:hanolamine 140-2 l,l-di (3,5-dibromo-4-hydroxy phenyl~ ethane diethanolamine lOS~10 " propylenediamine 175-8 2,4-dihydroxybenzophenone propylenediamine 212-18 3,5-dichlorosalicylaldehyde diethanolamine 100-5 hexamethyl phosphoramide 70-84 " propylenediamine 135-4S
bisphenol A disalicylate diethanolamine 150-5 " propylenediamine 155~75 tetrachlorohydroquinone diethanolamine 146-50 " propylene diam.ine 175-80 2-hydroxy-5-phenyl-propiophenone propylenediamine 180-5 2,4,6-tribenzoyl resorcinol diethanolamine 125-30 " propylenediamine over 280 3,5-dibromosalicylaldehyde diethanolamine 90-8 hexamethylphosphoramide 83-95 " propylenediamine 150-2 2-isopropyl-4,6-dinitro-phenol diethanolamine 105-10 " propylenediamine 188-90 3,4,6-trichloro-2-nitro phenol diethanolamine 146-50 " propylenediamine 185-90 1,1-methylenebis-2-naphthol diethanolamine 135-40 hexamethylphosphoramide 142-4 propylenediamine 160-5 1,1-di-2-naphthol diethanolamine 158~74 ' hexamethylphosphoramîde 112-20 ' propylenediamine 120-30 1,l-thio bis l2-naphthol3 diethanol~mine 135-42 " hexamethyl phosphoramide 124-8 " propylenediamine 120-5 p-chlorotrisphenol diethylene triamine 132-8 " hexamethylphosphoramide 149-Sl l,l-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane benzylamine 144-52 l,l-bis ~3,5-dichloro~4-hydroxy phenyl) cyclohexane diethanolamine 140-3 " diisopropyl ethanolamine 164-8 . dimethyl ethanolamine 169-85 " methyl diethanolamine 131 9 methyl ethanolamine 165-71 polyglycolamine ~-176 192-200 TABLE IV ~ Pa~e 12 Dissociation Phenol Am~ne Temp.C _ pentabromophenol aminoethylethanolamine 131-3 " 2-amino-2-methyl-1,3-propanediol 170-9 benzylamine 155-8 " diethanolamine 158-61 diisopropanolamine 178-37 diisopropyle~hanolamine 13a-3 N-ethyldiethanolamine93-8 methyl diethanolamine 120-3 " methyl ethanola~ne 163-5 " triethanolamine 129-34 hydroquinone acetamide 99-105 " . formamide 63-5 " morpholine 64-8 " piperazine 187-95 resorcinol hydrazine 48-55 " pipera~ine 147-52 pyrogallol formamide 55-8 " acetamide 58-65 e. Substrates The substrates used were a 25 lb/3000 sq. ft.
bleached sulfite paper and 3 mil polyester film.
f. Test equipment A thermal copier was used for reproduction and also for preparation of transparencies. A thermal matrix printer was used to demonstrate printing. A recorder was used to demonstrate chart recording capabilities.
The preferred embodiment of the invention is the use of a combination of color formers with a molecular complex of an amine and a phenolic compound and optionally an accel-erator. Stabilizers may also be used if so desired.
Preparation of Coatings The phenolic hydrogen bonded complexes are dispersed in a solution of a binder and ball-milled or otherwise ground until a fine particle size, preferably below 10 microns, is obtained. Any solvent-binder system may be used which does not dissolve and dissociate the phenolic complex. Some suit-able systems include water solutions of polyvinyl alcohol, hydroxyethyl cellulose, and other common water-soluble poly-meric resins. Methanol or ethanol solutions of nitrocellu-lose, ethylcellulose, and other alcohol-soluble resins canbe used. Likewise, hydrocarbon solutions of styrene polymers or copolymers, acrylate or methacrylate polymers or copolymers, hydrocarbon resins, elastomeric polymers, and the like, can 2~
~o~
~e u~ed-.- The limits for the concentration are governed by desirable coating viscosities, dry weight of the coating, and the like. Concentrations of complexes varyiny between 5 and 50 percent have been found to be convenient.
Similarly~ the leuco dye color-forming material is also dispersed by ball-milling or by other convenien~ means in a solvent-binder system which will not dissol~e and dis- .
sociate the pehnolic molecular complex. The r~active ingredients are ground separately in this case to permit the more convenient variation o the ratios of the co-reactin~ leuco dyes and phenolic complexes. ~owever~ this is nvt a requirement.as the leuco d~es and phenolic complexes have been grDund together without encountering any signs of mix instability or loss of the markin~ characteristics of the dried coating.. This is not true when the leuco dye~ for example Crystal Violet Lactone, is ground wi-t~ the free ~henolic material. The ground mixture ~ecomes hiyhly colored and is useless as a ~oatîng material~
Coatin~ ~pplications .
. The mix-tures.of gxinds of the leuco dyes and molecular ~omplexes of phenolic materials were applied by Meyer rod to a 25 lb/ 3000 s~.ft sulfite base paper and allowed to air~dry~
Dry coating weights of the thermosensi~ive coatings were varied from 1.5 lb/3000 s~.ft to over 10 lb/3000 sq~tO and useful records were made with each coating.
Specific Examples .
The ingredients are individually dispersed by ball-milling as a 15 percent concentration in a 5 percent solution -2~-of polyvinyl alcohol in water. These are combined in the ratios indicated in the -table and coated onto the substrate with a No. 16 wire wound Meyer rod and air dried. The coated substrates were imaged :in the test equipment to yive the colors indicated in the table.
COLOR PRECURSORS
Spiropyrans Code Base Aldehyde A 2-methylbenzothiazolium methyl tosylate 2-hydroxyl-1-naphthaldehyde B " " " salicylaldehyde C 5-chloro-2-methylene-1,3,3-trimethyl-indoline salicylaldehyde D " 5-nitrosalicylaldehyde E " 5-bromosalicylaldehyde F " 3,5-dibromosalicylaldehyde G 2-methylene-1,3,3-trimethylindoline 5-nitrosalicylaldehyde H " o-vanillin I 3-methyl-di-~ -naphthospiropyran Lactones J Crystal Violet lactone K 3,3-bis-p-aminophenylphthalide L 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide M Malachite Green lactone Cyclic Polyketones I Ninhydrin II EydrindantLn III Isatin IV Alloxan ~30-u o c~ a) ~ au u u ~ u u 0 ,-~
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Activators may be added to the heat-sensitive compo-sitions of the invention to lower the activation temper-atures of the above systems and to intensify the image mark. Some preferred activato:rs are ureas and ~hioureas such as phenylurea, phen~lthiourea and allylurea;
carbanilide; thiocarbanilide; zinc acetoacetonate; fatty acid salts of zinc such as zinc stearate and zinc palm-itate; and salicylanilde.
Dissociation Phenol ~mi~e 4,4'-isopropylidene bis-phenol di-n-propylamine 90-100 ethylenediamine 100-4 formamide 66 8 isobutylamine 88-93 methanediamine 128-30 N-methyliminobis~
propylamine 94-8 propylenediamin0 95-100 triethylenetetramine137-~
4,4'-thiobis (6-t.butyl-- m-cresol) t.butylamino~:ethyl methacrylate 62~5 cyclohexylamine 78-85 ethylenediamine 112-15 iminobispropylamine85~95 isopropylamine 164-6 propylenediamine 130-6 pyridine 160-5 triethanolamine 95-8 4,4'-butylidene bis (m-cresol) acatamine 82-3 benzylamine 135 cyclohexylamine 214-7 ethylenediamine 213-7 triethanolamin~ 68-70 2,2'-methylene bis (4-methyl-6-~.butylphenol) 2-amino-1-butanol 58-64 benzylamine 69-79 decylamine 52-3 1,3-diaminopropane 50-5 N-dibutylethylamine 60-5 diethanolamine 62-5 di-n-hexylamine 81-9 ethylcyclohexylamine92-4 N-ethyl diethanolamine 68-71 isopropylaminoiso-propylamine 128-32 ethylene diamine 54-8 hexamethyl phosphoramide 58-65 isoquinoline 121-5 N-methyldiethanolamine 127-34 methyl ethanolamine74-84 triamylamine 65-75 triethanolamine 61-5 p-cyclohexyl phenol triethanolamine 35 40 benzylamine 50-5 diethylenetriamine 70-85 ethylene diamine 125-30 hexamethyl phosphoramide 97-109 hydrazine 115-20 propylene diamine 88-90 o-cyclohexyl phenol benxylamine 82-95 ethylene diamine 88-93 hydrazine 75-80 ~0 TABLE IV - Pa~e 9 Dlssociation Phenol Amine Temp.C
p.t-butyl phenol benzylamine 70-80 ~thylenedi~mine70-3 " hydrazine 45-50 " propylenediamine 54-6 p-bromophenol formamide 35-8 2,4-dibromophenol benzylamine 80-5 2,4,6-tribromophenol t.butyl amin~ ethyl methacrylate 68-71 " benzylamine 125-30 " ethylene diamine 135-8 formamide 90-3 " hydrazine 145-54 " propylene diamine 87-92 Pentachlorophenol benzylamine 155-60 t.-butylaminoethyl methacrylate 115-20 diethanolamine145-55 " diethylenetriamine 185-90 " ethylenediamine115-20 " formamide 100-105 hexamethyl phosphoramide 79-83 " hydrazine ?00-205 propylenediamine 168-72 " triethanolamine133-7 2,6-dichlorophenol benzylamine 100-5 t.butylaminoethyl methacrylate 100-5 diethanolamine 83-6 " ethylenediamine110-15 " formamide 40-5 " hydrazine 115-20 " propylenediamine 115-25 2-chloro-4-phenyl phenol benzylamine 95-100 " ethylenedi~mine130-5 " hydrazine 108-12 " propylenediamine 50-4 tetrachlorophenol benzylamine 115-25 " t.butylaminoethyl methacrylate 95-100 " diethanolamine110-25 " ethylenediamine192-5 " formamide 85~90 " hydra2ine 163-5 " propylenediamine 165-70 " triethanolamine98-104 2,4,6-trichlorophenol benzylamine 120-5 " ~.bu~ylaminoethyl methacrylate 70-5 " ethylenediamine105-14 formamide 85-~0 hydrazine 150-7 " propylenediamine 100-5 2,4-dichloro-1-naphthol benæylamine 55-60 " diethanolamine65-70 ~9~
Dissociation Phenol Amine _Temp.C
2,4-dichloro-1-naphthol diethylenetriamine 79-83 formamide 78-82 hydrazine 83~93 2-naph`thol triethanolamine 63-5 " benzylamine 40-5 " ethylenediamine 86-9 formamide 56-59 " hydrazine llO-lZ
4,4-isopropylidene bis (p-chlorophenol) benzylamine 105-10 formamide 55-60 hexamethyl phosphvramide 46-8 hydrazine 100-112 2,6-dibromo-t.butyl phenol benzylamine 75-80 diethylenetriamine85-96 " ethylenediamine95-105 hydraxine 105-110 propylenediamine95-100 " triethanolamine104-6 p-phenoxy phenol ethylenediamine56-62 " hydraxine 48-56 2,4,5-trichlorophenol benezylamine 118-20 " t.butylaminoethyl methacrylate 55 60 diethanolamine 105-10 " diethylenetriamine 85-95 " ethylenediamine55-60 " - hydrazine 94-100 " propylenediamine96-104 l,l-di (4-hydroxyphenyl) cyclohexane diethanolamine100-112 " propylenediamine120-5 l,l-di (3,5-dibromo-4-hydroxy phenyl) cyclohexane diethanola~ine 149-54 " propylenediamine175-80 3,3-bis ~3,5-dibromo-4-hydroxy phenyl) pentane propylenediamine 183-g2 2,2-bis (3,.5-dibr~mo-4-hydroxy phenyl) pentane diethanolamine 110-18 " propylenediamine180-90 bis (3,5-dibromo-4-hydroxy phenyl) methane diethanolamine 115-23 2,2-bis ~3,5-dibromo-4-hydroxy phenyl) butane diethanolamine 142-5 " propylenediamine174-6 3,3'-5,5'-tetrabromo-4,4'-dihydroxy biphenyl diethanolamine 173-80 l-phenyl-l, l-di (3,5-di-bromo-4-hydroxy phenyl) ethane diethanolamine 145-50 " propylenediamine . 185-200 2,2-di (3,5-dibromo-4-hydroxypheny].) 4-methyl-penetane diethanolamine 115-20 " propylenediamine190-4 T~BLE IV ~ Page 11 Dissociation Phenol Amine Tem .~C
P _ ._ 2,2-di (3,5 di~romo-4~
hydroxy phenyl) heptane diethanolamine 145-50 " prop~ylenediamine 195-7 l,l-di (3,5-dibromo-4-hydroxy phenyl) butane diethanolamine 100-15 " propylene diamine 173-7 2,2-di (3,5-dibromo-4-hydroxy phenyl) octane diet:hanolamine 140-2 l,l-di (3,5-dibromo-4-hydroxy phenyl~ ethane diethanolamine lOS~10 " propylenediamine 175-8 2,4-dihydroxybenzophenone propylenediamine 212-18 3,5-dichlorosalicylaldehyde diethanolamine 100-5 hexamethyl phosphoramide 70-84 " propylenediamine 135-4S
bisphenol A disalicylate diethanolamine 150-5 " propylenediamine 155~75 tetrachlorohydroquinone diethanolamine 146-50 " propylene diam.ine 175-80 2-hydroxy-5-phenyl-propiophenone propylenediamine 180-5 2,4,6-tribenzoyl resorcinol diethanolamine 125-30 " propylenediamine over 280 3,5-dibromosalicylaldehyde diethanolamine 90-8 hexamethylphosphoramide 83-95 " propylenediamine 150-2 2-isopropyl-4,6-dinitro-phenol diethanolamine 105-10 " propylenediamine 188-90 3,4,6-trichloro-2-nitro phenol diethanolamine 146-50 " propylenediamine 185-90 1,1-methylenebis-2-naphthol diethanolamine 135-40 hexamethylphosphoramide 142-4 propylenediamine 160-5 1,1-di-2-naphthol diethanolamine 158~74 ' hexamethylphosphoramîde 112-20 ' propylenediamine 120-30 1,l-thio bis l2-naphthol3 diethanol~mine 135-42 " hexamethyl phosphoramide 124-8 " propylenediamine 120-5 p-chlorotrisphenol diethylene triamine 132-8 " hexamethylphosphoramide 149-Sl l,l-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane benzylamine 144-52 l,l-bis ~3,5-dichloro~4-hydroxy phenyl) cyclohexane diethanolamine 140-3 " diisopropyl ethanolamine 164-8 . dimethyl ethanolamine 169-85 " methyl diethanolamine 131 9 methyl ethanolamine 165-71 polyglycolamine ~-176 192-200 TABLE IV ~ Pa~e 12 Dissociation Phenol Am~ne Temp.C _ pentabromophenol aminoethylethanolamine 131-3 " 2-amino-2-methyl-1,3-propanediol 170-9 benzylamine 155-8 " diethanolamine 158-61 diisopropanolamine 178-37 diisopropyle~hanolamine 13a-3 N-ethyldiethanolamine93-8 methyl diethanolamine 120-3 " methyl ethanola~ne 163-5 " triethanolamine 129-34 hydroquinone acetamide 99-105 " . formamide 63-5 " morpholine 64-8 " piperazine 187-95 resorcinol hydrazine 48-55 " pipera~ine 147-52 pyrogallol formamide 55-8 " acetamide 58-65 e. Substrates The substrates used were a 25 lb/3000 sq. ft.
bleached sulfite paper and 3 mil polyester film.
f. Test equipment A thermal copier was used for reproduction and also for preparation of transparencies. A thermal matrix printer was used to demonstrate printing. A recorder was used to demonstrate chart recording capabilities.
The preferred embodiment of the invention is the use of a combination of color formers with a molecular complex of an amine and a phenolic compound and optionally an accel-erator. Stabilizers may also be used if so desired.
Preparation of Coatings The phenolic hydrogen bonded complexes are dispersed in a solution of a binder and ball-milled or otherwise ground until a fine particle size, preferably below 10 microns, is obtained. Any solvent-binder system may be used which does not dissolve and dissociate the phenolic complex. Some suit-able systems include water solutions of polyvinyl alcohol, hydroxyethyl cellulose, and other common water-soluble poly-meric resins. Methanol or ethanol solutions of nitrocellu-lose, ethylcellulose, and other alcohol-soluble resins canbe used. Likewise, hydrocarbon solutions of styrene polymers or copolymers, acrylate or methacrylate polymers or copolymers, hydrocarbon resins, elastomeric polymers, and the like, can 2~
~o~
~e u~ed-.- The limits for the concentration are governed by desirable coating viscosities, dry weight of the coating, and the like. Concentrations of complexes varyiny between 5 and 50 percent have been found to be convenient.
Similarly~ the leuco dye color-forming material is also dispersed by ball-milling or by other convenien~ means in a solvent-binder system which will not dissol~e and dis- .
sociate the pehnolic molecular complex. The r~active ingredients are ground separately in this case to permit the more convenient variation o the ratios of the co-reactin~ leuco dyes and phenolic complexes. ~owever~ this is nvt a requirement.as the leuco d~es and phenolic complexes have been grDund together without encountering any signs of mix instability or loss of the markin~ characteristics of the dried coating.. This is not true when the leuco dye~ for example Crystal Violet Lactone, is ground wi-t~ the free ~henolic material. The ground mixture ~ecomes hiyhly colored and is useless as a ~oatîng material~
Coatin~ ~pplications .
. The mix-tures.of gxinds of the leuco dyes and molecular ~omplexes of phenolic materials were applied by Meyer rod to a 25 lb/ 3000 s~.ft sulfite base paper and allowed to air~dry~
Dry coating weights of the thermosensi~ive coatings were varied from 1.5 lb/3000 s~.ft to over 10 lb/3000 sq~tO and useful records were made with each coating.
Specific Examples .
The ingredients are individually dispersed by ball-milling as a 15 percent concentration in a 5 percent solution -2~-of polyvinyl alcohol in water. These are combined in the ratios indicated in the -table and coated onto the substrate with a No. 16 wire wound Meyer rod and air dried. The coated substrates were imaged :in the test equipment to yive the colors indicated in the table.
COLOR PRECURSORS
Spiropyrans Code Base Aldehyde A 2-methylbenzothiazolium methyl tosylate 2-hydroxyl-1-naphthaldehyde B " " " salicylaldehyde C 5-chloro-2-methylene-1,3,3-trimethyl-indoline salicylaldehyde D " 5-nitrosalicylaldehyde E " 5-bromosalicylaldehyde F " 3,5-dibromosalicylaldehyde G 2-methylene-1,3,3-trimethylindoline 5-nitrosalicylaldehyde H " o-vanillin I 3-methyl-di-~ -naphthospiropyran Lactones J Crystal Violet lactone K 3,3-bis-p-aminophenylphthalide L 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide M Malachite Green lactone Cyclic Polyketones I Ninhydrin II EydrindantLn III Isatin IV Alloxan ~30-u o c~ a) ~ au u u ~ u u 0 ,-~
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Activators may be added to the heat-sensitive compo-sitions of the invention to lower the activation temper-atures of the above systems and to intensify the image mark. Some preferred activato:rs are ureas and ~hioureas such as phenylurea, phen~lthiourea and allylurea;
carbanilide; thiocarbanilide; zinc acetoacetonate; fatty acid salts of zinc such as zinc stearate and zinc palm-itate; and salicylanilde.
Claims (14)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A heat-sensitive recording composition com-prising (a) a phenol selected from Table IV of the specifi-cation;
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition, and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color con-trasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition, and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color con-trasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
2. The composition of claim 1, wherein said phenol and said amine or amide are combined in a hydrogen-bonded molecular complex.
3. The composition of claim 1, wherein said chromogenic compound is a lactone selected from Table I of the specification.
4. The composition of claim 1, wherein said chromogenic compound is a spiropyran selected from Table II
of the specification.
of the specification.
5. The composition of claim 1, wherein said cyclic polyketo compound is a compound selected from the group con-sisting of ninhydrin, hydrindantin, isatin, alloxan, and their homologs.
6. The composition of claim 1, wherein said amine or amide is selected from Table IV of the specification.
7. The composition of claim 1, and further com-prising an activator adapted to lower the temperature of color formation, said activator comprising a compound selected from the group consisting of ureas; thioureas; carbanilide;
thiocarbinalide; zinc acetoacetonate; fatty acid salts of zinc; and salicylanilde.
thiocarbinalide; zinc acetoacetonate; fatty acid salts of zinc; and salicylanilde.
8. The composition of claim 1, wherein said cyclic polyketo compound and said chromogenic compound are combined as an adduct.
9. A heat-sensitive recording composition com-prising (a) a phenol selected from Table III of the speci-fication;
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition; and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic com-pound being selected from the group consist-ing of lactone type leuco dyes and spiro-pyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition; and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic com-pound being selected from the group consist-ing of lactone type leuco dyes and spiro-pyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
10. The recording composition of claim 9, wherein said amine or amide is selected from Table IV of the specifi-cation.
11. A method for producing a heat-sensitive re-cording composition comprising the steps of dissolving a binder in a solvent in which complexes of a phenol and a complexing agent selected from the group consisting of amines and amides is insoluble, to form a binder-solvent solution, dispersing in said solution a chromogenic compound reactive with a phenol at elevated temperatures to develop a color contrasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiro-pyran type leuco dyes; a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition; and a hydrogen-bonded molecular complex of a phenol and a complexing agent selected from the group con-sisting of amines and amides, to form a dispersion, applying said dispersion to a substrate, and evaporating solvent from said dispersion to form a thermosensitive coating adapted to develop a color at elevated temperatures.
12. The method of claim 11 in which the phenol is one selected from those set out in Table IV of the specification.
13. The method of claim 11 or 12, wherein said cyclic polyketo compound is selected from the group consisting of ninhydrin, hydrindantin, isatin, alloxan, and their homologs.
14. A heat-sensitive recording composition comprising (a) a phenol reactive with an amine or an amide to form a hydrogen-bonded molecular complex;
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition, and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
(b) an amine or an amide;
(c) a mixture of heat-sensitive color precursors comprising:
(1) a cyclic polyketo compound reactive with amines and amides at elevated temperatures to form a color contrasting visibly with a background color of said composition, and (2) a chromogenic compound reactive with phenols at elevated temperatures to form a color contrasting visibly with a background color of said composition, said chromogenic compound being selected from the group consisting of lactone type leuco dyes and spiropyran type leuco dyes; and (d) binder means for binding the composition to a substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US774,385 | 1977-03-04 | ||
| US05/774,385 US4180405A (en) | 1977-02-25 | 1977-03-04 | Heat-sensitive recording composition with mixed color precursors |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099100A true CA1099100A (en) | 1981-04-14 |
Family
ID=25101073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA298,181A Expired CA1099100A (en) | 1977-03-04 | 1978-03-03 | Heat-sensitive recording composition with mixed color precursors |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS53110537A (en) |
| AU (1) | AU3382978A (en) |
| BR (1) | BR7801273A (en) |
| CA (1) | CA1099100A (en) |
| DE (1) | DE2809038A1 (en) |
| FR (1) | FR2382338A1 (en) |
| GB (1) | GB1563175A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151748A (en) * | 1977-12-15 | 1979-05-01 | Ncr Corporation | Two color thermally sensitive record material system |
| JPS5630894A (en) * | 1979-08-24 | 1981-03-28 | Mitsui Toatsu Chem Inc | Heat-sensitive recording sheet |
| US4500354A (en) * | 1982-09-27 | 1985-02-19 | Graphic Controls Corp. | Heat sensitive recording papers |
| US4675705A (en) * | 1985-06-10 | 1987-06-23 | Labelon Corporation | Heat sensitive coating |
-
1978
- 1978-02-20 GB GB663678A patent/GB1563175A/en not_active Expired
- 1978-03-02 DE DE19782809038 patent/DE2809038A1/en not_active Withdrawn
- 1978-03-02 BR BR7801273A patent/BR7801273A/en unknown
- 1978-03-03 JP JP2441278A patent/JPS53110537A/en active Pending
- 1978-03-03 CA CA298,181A patent/CA1099100A/en not_active Expired
- 1978-03-03 FR FR7806238A patent/FR2382338A1/en active Granted
- 1978-03-03 AU AU33829/78A patent/AU3382978A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53110537A (en) | 1978-09-27 |
| DE2809038A1 (en) | 1978-09-07 |
| FR2382338B3 (en) | 1980-12-05 |
| AU3382978A (en) | 1979-09-06 |
| BR7801273A (en) | 1979-04-03 |
| GB1563175A (en) | 1980-03-19 |
| FR2382338A1 (en) | 1978-09-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |